Process of preparing wetting, sudsing, and detergent agents



Patented July 14, 1942 UNITED STATES PATENT OFFICE PROCESS OF PREPARING WETTING, SUDS- ING, AND DETERGENT AGENTS No Drawing. Application April 10, 1941, Serial No. 387,985

17 Claims.

This invention relates to a process for producing highly efiicient sudsing, emulsifying and detergent agents.

More specifically the present case relates to an improved process for the preparation of watersoluble salts of compounds of the following type twenty-two carbon atoms and R1 is an aliphatic hydrocarbon residue having two to four carbon atoms. These salts possess wetting, sudsing and detergent power in hard water and in accordance with my invention are produced by the condensation of a salt of a higher fatty acid with a low molecular weight halogensubstituted alkyl sulfonate in the presence of amides or substituted amides as more fully hereinafter set forth. a

It is an object of my invention to provide an improved method for the preparatio of the above compounds so that the resulting reaction product is freer of products of side reactions, contains a higher proportion of the desired prodnot, and under some conditions as described below may be used directly without purification as a washing agent of high efficiency in hard water.

It is a further object of my invention to provide a means whereby the above compounds can be manufactured economically and in good yields from soap and a halo-alkyl metal sulfonate, thus making unnecessary the use of the more costly fatty acid halides as starting materials.

Other objects of my invention will be apparent from the following description.

It is known that compounds coming within the classification above given, such as the sodium salt of the oleic acid ester of isethionic acid and the sodium saltof the coconut oil fatty acid ester of 1,2-dihydroxy propane sulfonic acid acid chlorides, it is obviously advantageous to use these in preference to the acid chloride. However, ordinarily such reactions as that of soap with halo-alkyl sulfonates or the reaction of fatty acids with hydroxy-alkyl sulfonates progress slowly even at temperatures in the neighborhood of 200 C. Consequently in prior methods for wherein RC is an acyl radical having eight to I producing detergent and sudsing agents of the type here under consideration from soap or free fatty acid, purification of the resulting product of the condensation by crystallization from solvents has been necessary for one of two reasons. Either the product contains unreacted harmful soap because of too short a time of reaction or too low a reaction temperature, or the product contains harmful by-products including decomposition products and dark colored materials because of too long a reaction time or too high a reaction temperature. In either case the impurity is deterimental to the performance of the product as a cleansing agent and as far as I am aware there is no happy medium in which to operatefandobtain an active product resistant to hard water and acids without subjecting the re action product to expensive and time consuming purification including crystallization from a suitable solvent.

In accordance with the present invention, the reaction between the soap and the halogen substituted sulfonate is brought nearer theoretical completion by the use of a reaction medium consisting essentially of certain amides or substituted amides, or mixture of same, derived from monocarboxylic acids, which reaction medium is volatilizable at a temperature below that at which harmful decomposition products are formed, such as for example temperatures not substantially higher than C. The products of my invention at most contain only inconsequential quantities of unreacted soap. In addition the use of the amide or substituted amide reaction medium materially reduces the time and temperature of reaction to bring about suitable formation of the desired product and this also gives an improved result since reduction in reaction time and temperature reduces decomposition and the formation of by-products which are detrimental to the performance of the material as a washing agent in hard water. Thus in the practice of my invention a product is obtained which may be used in washing operations directly without purification with excellent results provided the presence of the amide or substituted amide is not objectionable from an odor, appearance or consistency standpoint and provided further that it is not harmful to the performance of the detergent in aqueous solution. As a rule those amides and substituted amides Which are water soluble are not detrimental and need not be removed from the reaction product unless other properties make separation essential or advisable.

Purification of the products of my invention is necessary therefore only in case the presence of the amide or substituted amide is undesirable. If such is the case removal of this reaction medium may be easily and readily accomplished mere 1y by volatilizing at atmospheric or subatmosand detergent agent.

m1; a and attendantdisadvantages such as low of yield and costly operation are therefore avoided.

The highly advantageous action of the reaction medium in the n of detergents of the type herein referred to is not due solely to any solvent action which the amide may have, because I have found that ethylene glycol, which is an excellent solvent for both reactants. does not funcfloninthesamemannerasthe amide or substituted amide but, in contrast thereto, results in a lower yield of a reaction product which is contaminated so highly with unreacted soap and other detrimental impurities that purification by crystallization from a solvent is essential in order to obtain an eflicient wetting, sudsing Apparently the amide or substituted amide a characteristic or combination of character. ,tics, such as a catalytic eilect in tion with a solvent eifect, make ing this type of compound especially suitable for thepurposeathandbecauseas farasIam aware there is no other compound which functions in the same manner as the amides and subsidtuted amides covered herein to give the highly advantageous result of the present invention.

In the preferred practice of my invention, the fatty acid soap is heated with the halogen substituted sulfonate in the presence of a sufilcient amount of amide or substituted amide as the re action medium to allow the formation of a fluid reaction mix at elevated temperature. Under such conditions a substantial part of the reactants is in solution. Aiter the reaction has reached substantial completion, as may be determined by the discontinuance of the precipitation of neutral salt or the complete solution or the product in hard water, the reaction medium may be removed by distillation from the mixture at atmospheric pressure or subatmospheric pressure but at a temperature below that at which the reactants or products decompose. The residue consists predominantly of the desired detergent product and is suficiently active in sudsing and detergent power that it may be used directly without further Imrification in washing or laundering operations. of course purification from a solvent may be eflected if desired.

My invention will be more clearly imderstood from the following examples in which specific conditions of operation are set forth. However, the invention is not limited to those specific conditions as more particularly pointed out herein- Kmmple 1.-115 parts of sodium soap derived from coconut oil are mixed with 100 parts of sodium monochlorhydrin sulfonate and 150 parts of acetamide in a reaction vessel which is not attached by the reactants, such as a glass-lined vessel for example. The mixture is heated with stirring at 145 C. for two hours, after which most of the acetamide is removed by distillation under Woman at 140 C. A product so prepared ocvinvv excellent sudsing and detergent characteristics in hard water containing the equivalent of 21 grains CaC'Oa per U. 8. gallon.

Example 2.5 parts sodium monochlorhydrin sulfonate and 6 parts sodium coconut oil soap were heated at 150 C. for two hours in the presence of 5 parts benzamide. The unpurified product disolved completely in unaffected by hardness and acid.

Example 3.6 parts of the potassium salt of beta methyl monochlorhydrin suli'onate and 7 parts potassium-oleate were heated at 145 C. for 3 hours in the presence 01' 8 parts acetanilide. The unpurified product dissolved completely in hard water to yield a solution which possessed excellent sudsing, detergent and wetting power.

Example 4.42 parts magnesium laurate, 39 parts of sodium monochlorhydrin sulfonate and parts acetamide were mixed and heated with agitation at about C. for two hours. The reaction product was purified by a single crystallization from alcohol. The purified material was obtained in good yield and an aqueous solution thereof was clear and foamed profusely in the presence of acids and of hardness imparting constituents. 7

Example 5.23 parts of coconut oil sodium soap, 21 parts of the potassium salt of beta methyl monochlorhydrin sulfonate and 20 parts of diethyl lauramide are mixed and heated together in a reaction vessel for four hours at about C. The product thus obtained has excellent wetting, sudsing and detergent power in hard water.

In the above examples I have shown how my invention may be practiced with commonly occurring materials. However, while these examples express probably the most practical way of carrying out my process, other materials may be employed. For example, while I have shown the use of coconut oil soap, oleic acid soap and lauric acid soap in the examples, soaps of other fatty acids, individually and in admixture, having eight to twenty-two carbon atoms may be employed. Thus if desired, the stearates, palmitates, or myristates, or soaps from any of the naturally occurring vegetable and animal fats and oils may be used. 7 Also, it should be noted that in addition to alkali metal soaps, alkaline earth metal soaps such as calcium and magnesium soaps, or even some heavy metal soaps, may be used provided the metal is such that it readily combines with the halogen of the halogen substituted sulfonate to produce a neutral salt.

In the examples, I have shown throughout the use of chlorine substituted sulfonates merely because these derivatives are readily available or easily prepared. However, a sulfonate substituted with any other halogen, such as bromine, may be employed with equal case without departing from the spirit of the invention.

The kind of metal ion in the halogen substituted sulfonate salt is relatively unimportant as long as the ultimate detergent agent, that is the condensation product, is water-soluble. Thus, for example, the alkali metals sodium and potassium and the alkaline earth metals calcium and magnesium may be employed since they form salts which are soluble in hard water. For obvious reasons I prefer .to employ the same metal as that of the soap used in the reaction.

The intermediate sulfonates, that is thehalogen substituted sulfonates, coming within the scope of the present invention are those aliphatic compounds having, as above stated, two to four carbon atoms. Thus the following compounds in addition to those given in the examples may be employed: potassium monochlorhydrin sulronate. sodium beta methyl monochlorhydrin suli'onate, sodium chlorethyl sulfonate, chloro olefin sulionic acids such as z-chloromethyl propene sodium sulfonate and others which will be readily apparent to those versed in the art.

' It has been stated above that the amides or substituted amides which may be employed in my moo-N in which R2 is alkyl, aryl or hydroxy alkyl and R3 and R4 are radicals selected from the group consisting of hydrogen, alkyl, aryl, hydroxy alkyl and alkylene joined through an oxygen atom (Ra-O-R4).

Specific examples of amides and substituted amides which may be employed in accordance with my invention are the following:

Acetamide H CHa-C'NHz Benzamide I onto-N Acetanllide Propionamide Butyramide II C 3H7- O -NH: Isobutyramide I CH3 Diethyl acetamide O CzHs cm-o-N Ethanolacetamide II CHa-C-N C2H5OH Hydroxy acetamide our-( 5 -NH2 Diethyl caprylamide O CzHi CzHs Dibutyl lauramide ll OuHza- C-N CAHD C 4H0 Ethanol lauramide o C 11H2a- -N QZHaOH Acetyl morpholine CHsCN The preferred temperature range within which to carry out the condensation reaction is 140 to 150 0., but of course the condensation may be carried out at temperatures outside of these limits. For example, some reaction is evident at temperatures as low as 130 C. and such low temperatures may be fully sufficient in some instances. Of course temperatures higher than 150 C. may also be employed, but temperatures substantially above 175 C. are usually unnecessary and may even be harmful since such high temperatures favor decomposition and the production of undesirable byproducts.

The amount of amide or substituted amide which should be employed is not very critical. In my work I have found that the minimum amount of reaction medium is about one half the weight of the mixture of soap and halogen substituted alkyl sulfonate. Ordinarily I employ an amount of reaction medium which is equal to the combined weights of soap and sulfonate, but of course the amount employed may be much larger, even four to six times the weight if such usage is desired. An excess is not harmful.

Having thus described my invention, what I claim and desire to secure by Letters Patent is:

1. In the process of producing a wetting, sudsing and detergent agent of the general formula wherein 3-00 is the acyl radicalof a fatty acid having eight to twenty-two carbon atoms, R1 is a radical selected from the group consisting of alkylene and hydroxy alkylene radicals having two to four, carbon atoms and Me is a metal forming a water-soluble salt, the step which consists in condensing a metal salt of a fatty acid having eight to twenty-two carbon atoms with a halogen substituted sulfonate of the general formula X-Rr-SOsMe wherein X is halogen, and R1 and Me are as above indicated, in the presence of a reaction medium of the group consisting of amides and substituted amides of the formula fi) /Ra R2.C.N

wherein R2 is a radical of the group consisting of alkyl, aryl, and hydroxy alkyl and Re and R4 are selected from the group consisting of hydrogen, alkyl, aryl, hydroxy alkyl and alkylene joined through an oxygen atom, the said reaction medium being one which does not enter into the reaction and being volatilizable at a temperature below that at which harmful decomposition products are formed in the reaction mix.

2. The process of claim 1 in which the reaction medium is an unsubstituted amide.

3. The process of claim 1 in which the reaction medium is acetamide.

4. The process of claim 1 in which the fatty acid salt is sodium coconut oil soap and the halogen substituted sulfonate is monochlorydrin sodium sulfonate.

5. The process of claim 1 in which the fatty acid salt is sodium coconut oil soap; the halogen substituted sulfonate is monochlorhydrin sodium sulfonate, and the reaction medium is acetamide.

6. The process of claim 1 in which the reaction medium is an N- mono substituted amide.

'7. The process of claim 1 in which the reaction medium is an N- mono substitute acetamide.

I I 8. Theprocess of claim '1 in which the reaction medium is N-ethyl acetamide. I I

9. The process of claim 1 in which the fatty acid salt is sodium oleate and the halogen substituted sulfonate is 'monochlorhydrin sodium 7 sulfonate. I

10. The process of-claim 1 in which the fatty acid salt is sodium oleate, the halogen substituted sulfonate is monochlorhydrin sodium sulfonate and the reaction medium is N-ethyl acetamide. I I

11. The process of claim 1 in which the reac-' tion medium is anN,N- disubstituted amide.

' 12. The process of claim 1 in which the reaction medium is a disubstituted acetamide.

halogen substituted sulfonate is, beta methyl monochlorhydrin sodium sulfonate.

15. The process of claim 1 inwhich the fatty acid salt is sodium coconut oiisoap, the halogen substituted sulfonate is beta methyl 'm'onochlorhydrin sodium sulfonate and the reaction'medium is diethyl acetamide.

16. In thetprocess of producing a wetting,

sudsing and detergent agent of the general formula I R-CO-ORrSOcMe v where R-CO'is the acyl radical of a fatty acid having eight-to twenty-two carbon atoms, R1 is a radical selected from the group consisting of alkylene and hydroxy alkylene radicals having two to four carbon atoms and Me is a metal forming a water soluble salt, the step which consists in condensing a metal salt of a i'atty acid having eight to twenty-two carbon atoms with a halogen substituted sulfonate of the general formula X-Rr-SOaMe where X is halogen and R1 and Me are as above indicated, in the presence of about fifty per cent to about one hundred per cent, based on the mixture of fatty acid salt and halogen substituted sulfonate, of a reaction medium of the group consisting of amides and substituted amides of the formula where R: is a radical of the group consisting of alkyl, aryl and hydroxy alkyl, and Re and R4 are selected from the group consisting of hydrogen, alkyl, aryl, hydroxy alkyl and alkylene joined through an oxygenatom. the said reaction medium' being one which does not enter into the reaction and being volatilizable at a temperature below that at which harmful decomposition prod- R-CO-ORr-SOsMe I where RC0 is the acyl radical of a fatty acid having eight to twenty-two carbon atoms, R1 is a radical selected from the groupconsisting of alkylene and hydroxy: alk'ylene radicals having two' to four carbon atoms and Me is a metal forming a water soluble salt, the steps which consist in condensing a metal salt of a fatty acid having eight to twenty-two carbon atomswith a halogen substituted sulfonate of the general formula I where X is halogen and R1 and Me are as above indicated, in the presence of about fifty per cent I I to about one hundred per cent, based on the mixture'of fatty acid salt and halogen substituted sulfonate, of a reaction medium of thegroup, consisting .of amides and substituted amides of the formula being volatilizable at a temperature below that NATHANIEL BEVERLEY TUCKER. 

